Ketoxime carbamates

ABSTRACT

Carbamate derivatives of ketoximes are useful in combatting pests such as insects, mites, and nematodes.

CROSS REFERENCE TO RELATED APPLICATION

This application is a continuation-in-part of copending application Ser.No. 229,207 filed Feb. 24, 1972, now U.S. Pat. No. 3,875,232 thespecification and claims of which are specifically incorporated hereinby reference, said application Ser. No. 229,207 being acontinuation-in-part of application Ser. No. 32,584 filed Apr. 8, 1971,now abandoned.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to organic compounds useful as pesticides andmore particularly to carbamate derivatives of ketoximes havinginsecticidal, miticidal, and, in some cases, nematocidal activitycomparable or superior to the most closely related commercial productswhile having significantly lower toxicity toward mammals than thosecommercial products.

2. Description of the Prior Art

The outstanding pesticidal activity of the carbamate derivatives of theketoximes disclosed in this invention is surprising and unexpectedbecause the prior art indicates that carbamate derivatives only ofsubstituted aldoximes have high pesticidal activity, whereas ketoximederivatives were essentially inactive. For example, U.S. Pat. No.3,217,037 and U.S. Pat. No. 3,507,965 show compounds, possessingpesticidal activity, of the structure: ##STR1## wherein X== O orS(O)_(n) when n= 0, 1, or 2 and the free valences are satisfied byhydrogen or hydrocarbyl radicals. In these two patents, the preferredcompounds are aldoximes wherein the carbon atom (C₁) attached to theoxime moiety in the above structure is substituted with hydrogen. In theJ. Agr. Food Chem., 14, 356 (1966), the patentees of these patentsstate, "The data . . . demonstrate . . . the detrimental effect . . . ofreplacing the aldehydic hydrogen with an alkyl group. All of theketoxime derivatives . . . were virtually inactive when compared withthe aldoxime derivative . . . " Ketoxime compounds of Formulas (I) and(II) below are reported in the reference as being essentially inactivecompared to the aldoxime compound of Formula (III) below which is knowncommercially as aldicarb (Temik). The compound of Formula (II) differsfrom the compound of Formula (III) only in that a methyl group has beensubstituted for the aldehydic hydrogen of Formula (III). ##STR2##

The ketoxime compounds of Formulas (I) and (II) have been resynthesizedand tested and their reported lack of activity relative to that of thecompound of Formula (III) reconfirmed. Surprisingly, however, theketoxime derivatives of the present invention have been found to possesshigh pesticidal activity, comparable or superior to that of the compoundof Formula (III).

SUMMARY OF THE INVENTION

The carbamates of ketoximes of the present invention can be representedby the formula: ##STR3## where: R₁ = R₂ -R₃ or X;

R₂ -r₃ = hydrogen, lower alkyl, lower alkenyl, lower alkynyl,substituted lower alkyl, alkenyl, or alkynyl with the proviso that R₂and R₃ may be connected to form a cycloaliphatic ring;

R₄ -r₅ = hydrogen;

R₆ -r₇ = hydrogen, lower alkyl, lower alkenyl, or lower alkynyl;

X= sr₈, s(o)r₈, so₂ r₈, or₈, oso₂ r₈, nr₈ r₉, no₂, cn, scn, n₃, orhalogen;

R₈ = hydrogen, lower alkyl, lower alkenyl, lower alkynyl, aryl,substituted aryl, carbamyl, substituted carbamyl, acyl, or substitutedacyl with the proviso that the lower alkyl or alkenyl groups may befurther substituted with X; and

R₉ = hydrogen or lower alkyl with the proviso that R₈, R₉ and N in theNR₈ R₉ group may form a heterocyclic ring.

The term lower alkyl radical means a radical having from one to aboutseven carbon atoms.

This invention specifically includes those carbamates of Formula (IV)where R₂ and R₃ are lower alkyl radicals such as methyl; R₁ is hydrogen,or X; R₆ and R₇ are individually hydrogen, a lower alkyl radical such asmethyl or a lower alkenyl radical; X is --S(O)_(n) R₈ --Y where n= 0, 1,or 2; R₈ is a lower alkylene radical; and Y is selected from the groupconsisting of SR₉, S(O)R₉, SO₂ R₉, OSO₂ R₉, SCN, haloalkyl, alkoxy,acyl, alkoxy carbonyl, carboxylate, and carboxyl; with the proviso thatY, either alone, or in combination with R₈, can be in the form of acyclic radical, selected from the group consisting of thiophene,thiazine, pyridene, and R₉ is selected from the group consisting ofhydrogen, lower alkyl, lower alkenyl, lower alkynyl, aryl, carbamyl,acyl, or haloalykl.

It is completely unexpected to discover that carbamate derivatives ofketoximes such as carbamate of Formula (V) have pesticidal activitycomparable to that of the carbamate derivative of the aldoxime ofFormula (III): ##STR4## and simultaneously exhibit significantly lowertoxicity toward mammals than does the compound of Formula (III). Thus,the oral toxicity of the compound of Formula (V), measured on albinorats and expressed as the LD₅₀, was found to be 8.5 mgm/kg of bodyweight; the dermal toxicity, measured on albino rabbits, again expressedas the LD₅₀, was 38.9 mgm/kg of body weight. LD₅₀ is a standard means ofexpressing toxicity and indicates the concentration required to kill 50%of the test animals. In each case, the LD₅₀ value is approximately eighttimes greater than the reported value for the carbamate derivative ofthe aldoxime compound of Formula (III).

It is an object of this invention to provide carbamates of substitutedketoximes, which are useful pesticides. A further object is to provide amethod for producing these carbamates. Another object is to providepesticidal compositions containing these carbamates. Still anotherobject is to provide methods of controlling pests such as insects,mites, and nematodes using these carbamates. It is intended, however,that the detailed description and specific examples given herein do notlimit this invention but merely indicate preferred embodiments thereofsince various changes and modifications within the scope of thisinvention will become apparent to those skilled in the art.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Preferred compounds of Formula (IV) include those carbamates of Formula(IV) where R₂ and R₃ are lower alkyl radicals such as methyl; R₁ is R₂or hydrogen; R₆ and R₇ are individually hydrogen, a lower alkyl radicalsuch as methyl or a lower alkenyl radical; X is --OR₉ or --S(O)_(n) R₈--Y where n = 0, 1, or 2; R₈ is a lower alkylene radical; and Y isselected from the group consisting of SR₉, S(O)R₉, SO₂ R₉, OSO₂ R₉, SCN,haloalkyl, alkoxy, acyl, alkoxy carbonyl, carboxylate, and carboxyl;with the proviso that Y, either alone, or in combination with R₈, can bein the form of a cyclic radical, selected from the group consisting ofthiophene, thiazole, pyridine; and R₉ is selected from the groupconsisting of hydrogen, lower alkyl, lower alkenyl, lower alkynyl, aryl,carbamyl, acyl, or haloalkyl.

These compounds exhibit extremely high activity as insecticides andmiticides, both as contact and as systemic toxicants. In some cases,they show high nematocidal activity.

As specific examples of these compounds, there may be mentioned1-hydrocarbylthio-3,3-dimethyl-2-methylcarbamyloximinobutanes such as:

3,3-dimethyl-2-methylcarbamyloximino-1-(2-methylthioethylthio)-butane;

1-(2-ethylthioethylthio)-3,3-dimethyl-2-methylcarbamyloximino-butane;

1-(2-methoxyethylthio)-3,3-dimethyl-2-methylcarbamyloximino-butane;

1-(2-ethoxyethylthio)-3,3-dimethyl-2-methylcarbamyloximino-butane;

3,3-dimethyl-2-methylcarbamyloximino-1-(3,3,3-trifluoropropylthio)butane;

1-(3,3,3-trichloropropylthio)-3,3-dimethyl-2-methylcarbamyloximinobutane;

1-(2-cyanoethylthio)-3,3-dimethyl-2-methylcarbamyloximinobutane;

Additional examples of these compounds include those wherein two membersof the group R₁, R₂ and R₃ are joined together to form a ring as, forexample:

1-cyclopropyl-1-methylcarbamyloximino-2-(methylthioethylthio)ethane;

1-methylcarbamyloximino-1-(1-methylcyclopropyl)-2-(methylthioethylthio)ethane;

1-cyclobutyl-1-methylcarbamyloximino-2-methylthiomethylthioethane;

1-methylcarbamyloximino-1-(1-methylcyclobutyl)-2ethylthiomethylthioethane;

1-cyclopentyl-1-methylcarbamyloximino-2-(ethylthioethylthio)ethane;

1-cyclohexyl-1-methylcarbamyloximino-2-(methylthioethylthio)ethane;

Still further examples of these compounds include:

1-tert.-butylthioethylthio-3,3-dimethyl-2-methylcarbamyloximinobutane;

1-sec.-butylthiomethylthio-3,3-dimethyl-2-methylcarbamyloximinobutane;

1-isobutylthioethylthio-3,3-dimethyl-2-methylcarbamyloximinobutane;

1-vinylthioethylthio-3,3-dimethyl-2-methylcarbamyloximinobutane;

1-(2-propenylthiomethylthio)-3,3-dimethyl-2-methylcarbamyloximinobutane;

1-(3-butenylthiomethylthio)-3,3-dimethyl-2-methylcarbamyloximinobutane;

1-ethynylthiomethylthio-3,3-dimethyl-2-methylcarbamyloximinobutane;

1-phenylthiomethylthio-3,3-dimethyl-2-methylcarbamyloximinobutane;

1-benzylthioethylthio-3,3-dimethyl-2-methylcarbamyloximinobutane;

and the like;

It will be appreciated by those skilled in the art that the ketoximederivatives of this invention may exist in two geometric forms, the synand the anti, representing the cis and trans isomers around the oximedouble bond. Both isomers and their mixtures are intended to be includedin the scope of this invention.

These compounds can be prepared by one of several methods. The onemethod (herein referred to as Method A) involves reaction of anisocyanate with an oxime as shown, for example, in the equation:##STR5## wherein R₁ through R₆ and X are defined above. The oxime andisocyanate are reacted in an inert organic from about 0° C. to about150° C., preferably from about 20° to about 80° C., and at a pressurefrom about 1 to 10 atmospheres, preferably from about 1 to about 3atomspheres. Reaction pressure is determined by reaction temperature,concentration and vapor pressure of the isocyanate.

Any inert organic solvent used in the reaction should not containhydroxy, amino or other groups which will react with the isocyanatefunction. Useful inert solvents include aliphatic and aromatichydrocarbons, such as hexane, heptane, octane, benzene, toluene, xylene;ethers such as diethyl ether, dipropyl ether, ethylpropyl ether; esterssuch as ethyl acetate, ethyl propionate, ketones such as acetone, methylethyl ketone; and chlorinated hydrocarbons such as methylene chloride,perchloroethylene, and the like.

Preferably, reaction is carried out in the presence of from about 0.1 toabout 1.0% by weight, based on the weight of reactants, of a tertiaryamine catalyst such as triethyl amine, N,N-dimethylaniline, or the like.

The molar ratio of isocyanate to oxime can vary from about 0.1:1 toabout 10:1. An equimolar amount or slight excess of isocyanate ispreferred to ensure complete reaction of the oxime. Reaction times canvary from a few minutes to several days. Usually reaction times of fromabout 1/2 to about 6 hours are sufficient.

A second method (hereinafter referred to as Method B) for preparingthese compounds involves reaction of an oxime with phosgene to obtain anoxime chloroformate which is then reacted with an amine. This method isillustrated in Equations (1) and (2) below: ##STR6##

In the reaction shown in Equation (1), a solution of the oxime dissolvedin an inert solvent such as diethyl ether, is added slowly to a solutionof phosgene dissolved in an inert solvent in the presence of an HClacceptor such as a tertiary amine, e.g., N,N-dimethylaniline. Reactionis carried out from about -30° C. to about 100° C., preferably at fromabout 0° C. to about 50° C. The resulting reaction mixture, a solutionof the chloroformate in an inert organic solvent, can be filtered orwashed with water to remove amine hydrochloride before it is used in thereaction shown in Equation (2).

In the reaction shown in Equation (2), an amine is added to thechloroformate solution in the presence of an amine solvent such aswater, at temperatures between about -40° C. and about 80° C.,preferably at about 0° C. to about 40° C. A larger than molar excess ofamine can be used so that the amine acts both as reactant and as HClacceptor and complete conversion of chloroformate is obtained.Alternatively, a separate HCl acceptor, such as tertiary amine, can beused.

A third method (hereinafter referred to as Method (C) for thepreparation of the compositions of the present invention comprisesreacting:

(a) a compound of the formula ##STR7## wherein Z is a reactive halogen,and (b) HX,

in the presence of a HZ acceptor. This includes reaction of thehaloketones with mercaptans or alcohols in the presence of an acidacceptor, e.g., sodium alkoxide. Sulfinyl and sulfonyl linked compoundscan be prepared by oxidizing the appropriate sulfide linked compoundwith sodium metaperiodate or acidic hydrogen peroxide, respectively.

Liquid or solid carbamates produced by the above methods can berecovered from reaction mixtures by conventional means. For example,they can be recovered by removal of solvent and excess amine orisocyanate by vacuum distillation. Although these products are obtainedin very pure form, they can be further purified, if desired, byrecrystallization, distillation, absorption chromatography, or otherknown procedures.

Although the compounds of this invention can be applied in undilutedform to the plant or other material being treated, it is usuallydesirable to apply these compounds in admixture with either solid orliquid inert, pesticidal adjuvants. For example, the compounds can beapplied to plants for pesticidal purposes by spraying the plants withaqueous or organic solvent dispersions of the compounds. Choice of anappropriate solvent is determined by factors such as concentration ofactive ingredient, the volatility required in the solvent, cost of thesolvent, and nature of the material being treated.

Solvents, which can be employed as carriers for these compounds, whichhydrocarbons such as benzene, toluene, xylene, kerosene, diesel oil,fuel oil, and naphthas; ketones such as acetone, methyl ethyl ketone andcyclohexane; chlorinated hydrocarbons such as trichloroethylene,perchloroethylene; esters such as ethyl acetate, amyl acetate and butylacetate; ethers of glycol such as the monomethyl and monoalkyl ethers ofdiethylene glycol, the the monoethyl ether of propylene glycol; alcoholssuch as ethanol, isopropanol, pentanols, and the like.

These compounds can also be applied to plants and other materials inconjunction with inert solid adjuvants or carriers such as talc,pyrophyllite, attapulgite, chalk, diatomaceous earth, koalinite,montmorillonite, other silicates, silica, lime, calcium carbonate,certain organic carriers such as walnut shell four, wood flour, groundcorn cobs, and the like.

It is often desirable to use a surfactant (a surface active agent) inpesticidal compositions. An anionic, nonionic or cationic surfactant canbe used in the formulation of either solid or liquid compositions.Typical surfactants include alkyl sulfonates, alkylaryl sulfonates,alkyl sulfates, alkylamide sulfonates, alkylaryl polyether alcohols,fatty acid esters of polyhydric alcohols, ethylene oxide additionproducts of these esters; ethylene oxide addition products of long-chainmercaptans; sodium alkyl benzene sulfonates having 12 to 18 carbonatoms; ethylene oxide addition products of alkylphenols, such as phenolcondensed with 10 moles of ethylene oxide; cetyl pyridinium chloride;soaps such as sodium stearate and sodium oleate.

Solid and liquid formulations can be prepared by any suitable method.Solid active ingredients, in finely divided form, can be tumbledtogether with a finely divided solid carrier. Alternatively, the activeingredient in liquid forms such as solutions, dispersions, emulsions orsuspensions, can be admixed with the solid carrier in finely dividedform in amounts small enough to preserve the free-flowing property ofthe final dust compositions.

When solid formulations are used, in order to obtain a high degree ofcoverage with a minimum dosage, it is desirable that the formulation bein the form of a finely divided power or dust sufficiently fine thatsubstantially all of the solids will pass through a Tyler sieve having amesh size between about 20 and about 200.

In dust formulations, the active ingredient can be present in an amountof 5 to 50% of the total weight. However, concentrations outside thisrange are operative and compositions containing from 1 to 99% of activeingredient by weight are contemplated wherein the remainder is carrierand/or any other desired additive or adjuvant. It may be advantageous toadd a small amount of surfactant, e.g., 0.5 to 1% by weight based on thetotal weight of the dust formulation.

For spray application, the active ingredient may be dissolved ordispersed in a liquid carrier, such as water or other suitable liquid.The active ingredient can be added in the form of a solution,suspension, dispersion or emulsion in aqueous or nonaqueous medium.Desirably, 0.5 to 1.0% by weight of surfactant is present in the liquidcomposition.

For adjuvant purposes, any desired quantity of surfactant may beemployed, such as up to 250% by weight of the active ingredient. If thesurfactant is used only to impart wetting qualities to a spray solution,as little as 0.05% or less, by weight of the surfactant need be used.Larger quantities of surfactant are used because of biological behaviorof the surfactant rather than its wetting properties. Theseconsiderations are particularly important in the treatment of plants.The active ingredient in liquid formulations often may not be more than30% by weight of the total and may be 10% by weight or even as low as0.01% by weight.

For systemic application, it may be desirable to apply the pesticide tothe soil in the form of granules of an inert material coated with orincorporating the active ingredient. Reasons for the use of pesticidalgranules include elimination of water during application, reduction ofdrift, penetration through vegetative coverage, easy handling, storage,and increased safety to handlers of the pesticides. Useful granules basematerials include attapulgite, montmorillonite, corn cobs, walnutshells, and expanded vermiculites. Depending on their physicalproperties, the pesticides are either directly sprayed on the preformedgranular base or are dissolved in a suitable solvent and then sprayedonto the granular base after which the solvent is removed byevaporation. Granule base materials are usually 60 to 14 U.S. sieve sizeparticles, although other size particles may also be used.

Terms "pesticide" and "pesticidal" as used herein are intended to referto the killing and/or control of insects, mites, nematodes, or the like.It will be appreciated that application commonly referred to asinsecticidal, miticidal, nematocidal, or the like are contemplated inthe employment of these terms.

For a fuller understanding of the nature and objects of this invention,reference may be made to the following examples which are given toillustrate the invention and are not to be construed in a limitingsense. The infrared spectrum for each product described herein isconsistent with the assigned structure. All percentages, proportions,and quantities given in these examples are by weight unless otherwiseindicated. Likewise, all references to temperature are as °C. unlessotherwise indicated.

EXAMPLE 1 3,3-Dimethyl-1-tert.-butylthio-2-butanone (Compound 7569)

To a solution of 5.8 g (0.25 mol) of sodium metal in 175 ml of absoluteethanol is added, dropwise, 24.4 g (0.27 mol) of2-methyl-2-propanethiol. The stirred solution is heated for 20 minutes,cooled, and treated in a dropwise manner with 44.8 g (0.25 mol) of1-bromopinacolone, prepared according to the procedure of J. Am. Chem.Soc., 74, 4507 (1952). This reaction mixture is heated at reflux for 20minutes, cooled, and poured onto 200 g of ice and water. After beingsaturated with sodium chloride, the mixture is extracted with fourportions of ether. The combined ether extracts are dried over anhydrousmagnesium sulfate, filtered, and stripped of solvent. Distillation ofthe residue through a short Vigreaux column gives the desired product.Properties of this, and similar compounds prepared by substantially thesame procedure using the appropriate mercaptans and -haloketones, aregiven in Table 1.

EXAMPLE 2 3,3-Dimethyl-1-tert.-butylthio-2-butanone oxime (Compound7604)

A solution of 27 g (0.14 mol) of3,3-dimethyl-1-tert.-butylthio-2-butanone, 19.5 g (0.28 mol) ofhydroxylamine hydrochloride and 14.8 g (0.14 mol) of anhydrous sodiumcarbonate in a mixture of 200 ml of 95% ethanol and 110 ml of water isheated at reflux for 19.5 hours. Stripping of volatiles on a rotaryevaporator gives a slurry which is filtered to obtain the white solidoxime product. Properties of this and related compounds prepared bysubstantially the same procedure are given in Table 2. Where the oximeproduct is a liquid, isolation is accomplished by ethyl acetateextraction of the residue left after removal of the volatiles andsubsequent stripping of the dried extract.

EXAMPLE 3 Carbamate Preparation-- Method A

3,3-dimethyl-2-methylcarbamyloximino-1-tert.-butylthiobutane (Compound7619)

A solution of 4.7 g (0.023 mol) of3,3-dimethyl-1-tert.-butylthio-2-butanone oxime, 1.4 g (0.025 mol) ofmethyl isocyanate, and three drops of triethylamine in 35 ml ofanhydrous ether is heated at reflux for 16.5 hours. Stripping ofvolatiles on a rotary evaporator gives the desired product as a whitesolid. Properties of this and analogous compounds prepared bysubstantially the same procedure are given in Table 3.

EXAMPLE 4 Carbamate Preparation-- Method B

2-carbamyloximino-3,3-dimethyl-1-methylthiobutane (Compound 7859)

To a chilled solution of 5.4 g (0.055 mol) of phosgene in 50 ml ofanhydrous ether is added, dropwise, 6.1 g (0.05 mol) of N,N-dimethylaniline followed by a solution of 8.1 g (0.05 mol) of3,3-dimethyl-1-methylthio-2-butanone oxime in 50 ml of ether. Themixture is stirred for 2 hours, as it is allowed to come to roomtemperature, and then filtered. The chilled filtrate is treated over 15minutes with 10 ml (0.15 mol) of 29% aqueous ammonia. After beingstirred for additional 15 minutes, the organic layer is separated,washed with water, and dried. Stripping of solvent from the driedorganic layer gives 10.1 g of a clear liquid residue which solidifies onstanding. Properties of this and analogous compounds prepared bysubstantially the same procedure are shown in Table 3.

EXAMPLE 5 Carbamate Preparation--Method C

3,3-dimethyl-2-methylcarbamyloximino-1-(1-pyrrolidinyl)-butane (Compound7870)

To a solution of 12.6 g of1-bromo-3,3-dimethyl-2-methylcarbamyloximinobutane in 100 ml ofanhydrous ether is added, dropwise, 7.8 g (0.11 mol) of pyrrolidine. Themixture is stirred at room temperature for 1 hour and at reflux for 0.5hour, then cooled and washed with water. The ether solution isseparated, dried, and stripped of solvent to give 11.8 g of amber oilwhich solidifies on standing to an amber solid, m. 43°-46° C. Propertiesof this and analogous compounds prepared by substantially the sameprocedure are shown in Table 3.

EXAMPLE 6 3,3-Dimethyl-2-methylcarbamyloximino-1-methylsulfonyloxybutane(Compound 9350)

A solution of 7.5 g (0.04 mol) of1-hydroxy-3,3-dimethyl-2-methylcarbamyloximinobutane and 5.0 g (0.044mol) of methanesulfonyl chloride in 50 ml of benzene is treated dropwisewith 4.6 g (0.044 mol) of triethylamine with cooling to keep thetemperature below 35° C. After the addition, the stirred mixture isheated at 35° C. for two hours and then washed with aqueous sodiumbicarbonate and with water. The organic layer is dried over magnesiumsulfate, filtered, and stripped of volatiles to give 6.7 g (63%) ofamber, viscous liquid residue, n_(D) ²⁵ 1.4810.

Calc'd. for C₉ H₁₈ N₂ O₂ S: C, 40.6%; H, 6.8%; N, 10.5%; Found: C,41.2%; H, 6.8%; N, 10.5%.

EXAMPLE 7 3,3-dimethyl-2-methylcarbamyloximino-1-methylthiobutane(Compound 7268)

Compound No. 7268 was prepared using the following procedure:

3,3-Dimethyl-1-methylthio-2-butanone

To a solution of sodium ethoxide prepared from 7.7 g (0.33 mol) ofsodium metal and 200 ml of absolute alcohol was added 19 g (0.4 mol) ofmethanethiol over 10 min at ± 2° C. To this solution of thiomethoxidewas added dropwise, over 25 min. 59 g (0.28 mol) of1-bromo-3,3-dimethyl-2-butanone prepared according to the procedure ofJ. Am. Chem. Soc. 74, 4507 (1952). The temperature was maintained at 0°± 3° C. during the addition and for a further 30 min. The reactionmixture was filtered and the solvent removed by distillation. Vacuumdistillation of the residue gave the desired product as a colorlessliquid, b. 73° C./9.3 mm Hg, n_(D) ²⁴ 1.4650 in 54% pure yield.

3,3-Dimethyl-1-methylthio-2-butanone oxime

A solution of 20.4 g (0.14 mol) of 3,3-dimethyl-1-methylthio-2-butanone,19.6 g (0.28 mol) of hydroxylamine hydrochloride and 14.8 g (0.14 mol)of anhydrous sodium carbonate in 140 ml of 95% ethanol and 80 ml ofwater was heated at reflux for 16 hr. The resulting nearly colorlesssolution was stripped of volatiles on a rotary evaporator to yield a twolayered liquid residue. This residue was extracted with four portions ofethyl acetate. The organic extract was dried over magnesium sulfate,filtered from the drying agent and stripped of solvent. Distillation ofthe residue gave the desired product as a colorless liquid, b. 83°C./0.6 mm Hg, n_(D) ²² 1.4989.

Calc'd for C₇ H₁₅ NOS: C, 52.1; H, 9.4; N, 8.7; Found: C, 52.2; H, 9.4;N, 8.6.

3,3-dimethyl-2-methlcarbamyloximino-1-methylthiobutane

A solution of 110 g (0.68 mol) of 3, 3-dimethyl-1-methlthio-2-butaneoxime, 42.8 g (0.75 mol) of methyl isocyanate and three drops oftriethylamine in 400 ml of anhydrous acetone was heated at reflux for 16hr. Volatiles were removed by stripping on a rotary evaporator to give155 g of white solid residue, m 50°-53° C. A solution of 25 g of thisresidue in 200 ml of ether was washed with two 100 ml portions of water.The dried ether solution was reduced in volume to yield 12.6 g of whitecrystals, m 56.5°-57.5° C., which is the desired compound.

Calc'd for C₉ H₁₈ N₂ O₂ S: C, 49.5; H, 8.3; N, 13.0; Found: C, 49.3; H,8.9; N, 12.9.

In general, the sulfide compounds of the present invention will beoxidized, in situ during use, to the corresponding sulfoxide and then tothe corresponding sulfone. The oxidation can also be achieved by directsynthesis, as illustrated by Example 8.

EXAMPLE 8 3,3-Dimethyl-2-methylcarbamyloximino-1-methylsulfinylbutane(Compound 7804)

A stirred mixture of 9.0 g (0.042 mol) of sodium metaperiodate in 60 mlof water and 25 ml of methanol is cooled to 0° C. as 8.8 g (0.04 mol) of3,3-dimethyl-2-methylcarbamyloximino-1-methylthiobutane (compound7268--Example 7) is added in portions. After stirring a 0°-10° C. for 18hours, the mixture is allowed to warm to room temperature and strippedof volatiles on a rotary evaporator to give a residue which is extractedwith ethyl acetate. The dried extract is stripped to leave 9 g (96%) ofviscous yellow oil, the desired compound.

Calc'd. for C₉ H₁₈ N₂ O₃ S: C, 46.1% H, 7.7%; Found: C, 45.2%; H, 7.5%.

                                      TABLE 1                                     __________________________________________________________________________     ##STR8##                                                                     Compound                         Boiling Range                                                                        Refractive                                                                          Percent                                                                            Analysis                   Number                                                                              R.sub.1                                                                              R.sub.2                                                                           R.sub.3 X       in ° C/mm Hg                                                                  Index/° C                                                                    Yield                                                                              Calculated                                                                          Found                __________________________________________________________________________    7218  CH.sub.3                                                                             CH.sub.3                                                                          CH.sub.3                                                                           CH.sub.3 S 73/9.3 1.4650/24                                                                           62                              7443  CH.sub.3                                                                             CH.sub.3                                                                          CH.sub.3                                                                           CH.sub.3 OCOCH.sub.2 S                                                                   94/0.8 1.4720/24                                                                           64   C 52.9                                                                              C 52.6                                                                  H 7.9 H 7.5                7569  CH.sub.3                                                                             CH.sub.3                                                                          CH.sub.3                                                                           (CH.sub.3).sub.3 CS                                                                      84-92/9.8                                                                            1.4595/24                                                                           67   C 63.8                                                                              C 63.6                                                                  H 10.7                                                                              H 10.6               7573  CH.sub.3                                                                             CH.sub.3                                                                          CH.sub.3                                                                           CH.sub.2CHCH.sub.2 S                                                                     58-9/1.2                                                                             1.4762/24                                                                           24   C 62.7                                                                              C 62.8                                                                  H 9.4 H 9.1                7637  CH.sub.3                                                                             CH.sub.3                                                                          CH.sub.3                                                                           C.sub.6 H.sub.5 CH.sub.2 S                                                               104.5-106/                                                                           1.5306/24                                                                           57   C 70.2                                                                              C 70.9                                                0.5-0.6           H 8.2 H 9.0                7665  CH.sub.3                                                                             CH.sub.3                                                                          CH.sub.3                                                                           C.sub.6 H.sub.5 S                                                                        102/0.5                                                                              1.5425/24                                                                           38   C 69.2                                                                              C 70.0                                                                  H 7.7 H 7.7                7667  CH.sub.3                                                                             CH.sub.3                                                                          CH.sub.3 S                                                                         CH.sub.3 S 91-5/3.9                                                                             1.5138/23                                                                           56   C 47.2                                                                              C 46.8                                                                  H 7.9 H 7.8                7765.sup.(a)                                                                        CH.sub.3                                                                             CH.sub.3                                                                          CH.sub.3                                                                           C.sub.6 H.sub.5 O                                                                        106-8/1.8                                                                            1.5036/23                                                                           72     --    --                 7838  CH.sub.3                                                                             CH.sub.3                                                                          CH.sub.3                                                                           CH.sub.3 CH.sub.2 CH.sub.2 S                                                             49/0.3 1.4617/24                                                                           50   C 62.0                                                                              C 61.7                                                                  H 10.4                                                                              H 10.3               8126  (CH.sub.2).sub.5                                                                         CH.sub.3                                                                           CH.sub.3 S 86-7/0.8                                                                             1.4954/24                                                                           29   C 64.5                                                                              C 64.0                                                                  H 9.6 H 9.6                8373  (CH.sub.2).sub.2                                                                         H    CH.sub.3 S 71-4/7.8                                                                             1.4980/22.5                                                                         71   C 55.4                                                                              C 55.6                                                                  H 7.7 H 7.9                8504  (CH.sub.3).sub.3 C                                                                   H   H    CH.sub.3 S 68/4.8 1.4600/22                                                                           66   C 59.9                                                                              C 59.0                                                                  H 10.0                                                                              H 9.8                9011  (CH.sub.3).sub.2 CH                                                                  H   H    CH.sub.3 S 81/9.3 1.4610/23                                                                           76   .sup.(b)                   9275  CH.sub.3                                                                             CH.sub.3                                                                          CH.sub.3                                                                           CH.sub.3 CH.sub.2 SCH.sub.2 CH.sub.2 S                                                   110/0.3                                                                              1.5025/24                                                                           65   C 54.8                                                                              C 54.6                                                                  H 8.7 H 9.2                9278.sup.(c)                                                                        CH.sub.3                                                                             CH.sub.3                                                                          CH.sub.3                                                                           CH.sub.3 O 78/47  1.4136/23                                                                           57   C 64.5                                                                              C 64.3                                                                  H 10.8                                                                              H 10.8               9380  CH.sub.3                                                                             CH.sub.3                                                                          CH.sub.3                                                                           CF.sub.3 CH.sub.2 CH.sub.2 S                                                             60/0.08                                                                              1.4253/24                                                                           40   C 47.4                                                                              C 47.6                                                                  H 6.6 H 6.6                9382  CH.sub.3                                                                             CH.sub.3                                                                          CH.sub.3                                                                           Cl.sub.3 CCH.sub.2 CH.sub.2 S                                                            113/0.1                                                                              1.5055/24                                                                           39   C 40.0                                                                              C 40.2                                                                  H 5.4 H 5.5                9385  CH.sub.3                                                                             CH.sub.3                                                                          CH.sub.3                                                                            ##STR9##  72/0.08                                                                              1.5112/24                                                                           14   C 63.5                                                                              C 63.3                                                                  H 8.2 H 8.2                __________________________________________________________________________     .sup.(a) J. Am. Chem. Soc., 77, 3272 (1955)                                   .sup.(b) Ann. 672, 156 (1964)                                                 .sup.(c) J. Am. Chem. Soc., 72, 5161 (1950)                              

                                      TABLE 2                                     __________________________________________________________________________     ##STR10##                                                                    Compound                         Melting Point                                                                        Percent                                                                            Analysis                         Number                                                                              R.sub.1 R.sub.2                                                                           R.sub.3                                                                              X     in ° C                                                                          Yield                                                                              Calculated                                                                          Found                      __________________________________________________________________________    7252  CH.sub.3                                                                              CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3 S (a)    92     --    --                       7470  CH.sub.3                                                                              CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3 OCOCH.sub.2 S                                                                   --     87   C 49.3                                                                              C 49.4                                                                  H 7.7 H 7.7                                                                   N 6.4 N 6.2                      7604  CH.sub.3                                                                              CH.sub.3                                                                          CH.sub.3                                                                          (CH.sub.3).sub.3 CS                                                                      120-121                                                                              75   C 59.1                                                                              C 59.1                                                                  H 10.4                                                                              H 10.4                     7605  CH.sub.3                                                                              CH.sub.3                                                                          CH.sub.3                                                                          (CH.sub.3).sub.2 CHS                                                                     51-52  63   C 57.1                                                                              C 56.5                                                                  H 10.1                                                                              H 9.5                      7618  CH.sub.3                                                                              CH.sub.3                                                                          CH.sub.3                                                                          (CH.sub.3).sub.2 CHCH.sub.2 S                                                            (b)    38   C 59.1                                                                              C 59.2                                                                  H 10.4                                                                              H 10.5                     7682  CH.sub.3                                                                              CH.sub.3                                                                          CH.sub.3                                                                          C.sub.6 H.sub.5 CH.sub.2 S                                                               84-87  100  C 65.8                                                                              C 65.6                                                                  H 8.1 H 9.2                      7711  CH.sub.3                                                                              CH.sub.3                                                                          CH.sub.3                                                                          C.sub.6 H.sub.5 S                                                                        83-84  29   C 64.5                                                                              C 64.1                                                                  H 7.7 H 8.0                      7796  CH.sub.3                                                                              CH.sub.3                                                                          CH.sub.3                                                                          C.sub.6 H.sub.5 O                                                                        104-105                                                                              83   C 69.5                                                                              C 70.1                                                                  H 8.3 H 8.3                                                                   N 6.8 N 6.9                      7898  CH.sub. 3                                                                             CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.2CHCH.sub.2 S                                                                     57-58  56   N 7.5 N 7.3                      7925  CH.sub.3 CH.sub.2 CH.sub.2                                                            CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3 S (c)    --   N 7.4 N 7.4                      7946  CH.sub.3 S                                                                            CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3 S 70-75  75   C 43.5                                                                              C 42.8                                                                  N 7.8 N 7.8                      8154  (CH.sub.2).sub.5                                                                          CH.sub.3                                                                          CH.sub.3 S (d)    63   C 59.7                                                                              C 59.8                                                                  H 9.5 H 9.5                                                                   N 7.0 N 7.0                      8420  (CH.sub.2).sub.2                                                                          H   CH.sub.3 S (e)    95   N 9.7 N 9.5                      8872  CH.sub.3                                                                              CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3 SO.sub.2                                                                        73-75  40   N 7.3 N 7.2                      8873  CH.sub.3                                                                              CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3 S(O)                                                                            104-106                                                                              35   C 47.4                                                                              C 47.3                                                                  H 8.5 H 8.3                                                                   N 7.9 N 7.9                      9301  CH.sub.3                                                                              CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3 O (f)    45   C 57.9                                                                              C 57.6                                                                  H 10.4                                                                              H 9.9                      9302  CH.sub.3                                                                              CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3 CH.sub.2 O                                                                      (g)    74   N 8.8 N 8.6                      9332  CH.sub.3                                                                              CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3 CH.sub.2 SCH.sub.2 CH.sub.2 S                                                   42-45  81   C 51.1                                                                              C 51.1                                                                  H 9.0 H 8.9                                                                   N 6.0 N 5.8                      9381  CH.sub.3                                                                              CH.sub.3                                                                          CH.sub.3                                                                          F.sub.3 CCH.sub.2 CH.sub.2 S                                                             41-43  89   C 44.4                                                                              C 45.0                                                                  H 6.6 H 6.7                      9384  CH.sub.3                                                                              CH.sub.3                                                                          CH.sub.3                                                                          C.sub.6 H.sub.5 CH.sub.2 CH.sub.2 S                                                      48-50  98   C 66.9                                                                              C 67.8                                                                  H 8.4 H 8.5                      9430  CH.sub.3                                                                              CH.sub.3                                                                          CH.sub.3                                                                          SCH.sub.2 CH.sub.2 CCl.sub.3                                                             77-80  61   C 37.0                                                                              C 37.7                                                                  H 5.5 H 5.4                                                                   N 4.8 N 4.5                      9434  CH.sub.3                                                                              CH.sub.3                                                                          CH.sub.3                                                                           ##STR11## (1.5260/24)                                                                          31   C 58.4                                                                              C 57.1                                                                  H 8.1 H 8.2                                                                   N 7.6 N 7.8                      9876  CH.sub.3                                                                              CH.sub.3                                                                          CH.sub.3                                                                           ##STR12##  98-100                                                                              76   C 58.9                                                                              C 58.3                                                                  H 7.  H 7.3                                                                   N 12.5                                                                              N 12.4                     10567 CH.sub.3                                                                              CH.sub.3                                                                          CH.sub.3                                                                           ##STR13##   125-126.5                                                                          57   C 58.9                                                                              C 58.9                                                                  H 7.2 H 7.2                                                                   N 12.5                                                                              N 12.8                     __________________________________________________________________________     (a) n.sub.D.sup.25 1.4965                                                     (b) b. 104°  C/0.8 mm                                                  (c) n.sub.D.sup.24 1.4863                                                     (d) n.sub.D.sup.24 1.5164                                                     (e) n.sub.D.sup.23 1.5340                                                     (f) n.sub.D.sup.24 1.4460                                                     (g) n.sub.D.sup.24 1.4420                                                

                                      TABLE 3                                     __________________________________________________________________________     ##STR14##                                                                                                                    Melting Point                 Com-                                            in ° C                 pound                                           (Refractive                                                                          Analysis               No. R.sub.1                                                                              R.sub.2                                                                           R.sub.3                                                                            R.sub.6  R.sub.7                                                                          X          Method*                                                                            Index/° C)                                                                    Cal'd                                                                             Found              __________________________________________________________________________    7268                                                                              CH.sub.3                                                                             CH.sub.3                                                                          CH.sub.3                                                                           CH.sub.3 H  CH.sub.3 S A    50-52  C                                                                                 C 49.3                                                                    H                                                                                 H  8.9                                                                    N                                                                                 N 12.9             7472.sup.(a)                                                                      CH.sub.3                                                                             CH.sub.3                                                                          CH.sub.3                                                                           CH.sub.3 H  H          A    45-46  C                                                                                 C 55.8                                                                    H                                                                                 H  9.1             7503                                                                              CH.sub.3                                                                             CH.sub.3                                                                          CH.sub.3                                                                           CH.sub.3 H  H.sub.3 COCOCH.sub.2 S                                                                   A    (1.5016/23.5)                                                                        C                                                                                 C 48.0                                                                    H                                                                                 H  7.6             7577.sup.(a)                                                                      CH.sub.3                                                                             CH.sub.3                                                                          CH.sub.3 S                                                                         CH.sub.3 H  H          A    79     --  --                 7619                                                                              CH.sub.3                                                                             CH.sub.3                                                                          CH.sub.3                                                                           CH.sub.3 H  (CH.sub.3).sub.3 CS                                                                      A    105-106                                                                              C                                                                                 C 55.1                                                                    H                                                                                 H  9.3             7620                                                                              CH.sub.3                                                                             CH.sub.3                                                                          CH.sub.3                                                                           CH.sub.3 H  (CH.sub.3).sub.2 CHS                                                                     A    63-64  C                                                                                 C 53.6                                                                    H                                                                                 H  8.5             7639                                                                              CH.sub.3                                                                             CH.sub.3                                                                          CH.sub.3                                                                           CH.sub.3 H  (CH.sub.3).sub.2 CHCH.sub.2 S                                                            A    66-67  C                                                                                 C 55.2                                                                    H                                                                                 H  9.5             7702                                                                              CH.sub.3                                                                             CH.sub.3                                                                          CH.sub.3                                                                           CH.sub.3 H  C.sub.6 H.sub.5 CH.sub.2 S                                                               A    54-56  C                                                                                 C 61.1                                                                    H                                                                                 H  7.5             7718                                                                              CH.sub.3                                                                             CH.sub.3                                                                          CH.sub.3                                                                           CH.sub.3 H  C.sub.6 H.sub.5 S                                                                        A    106-107                                                                              C                                                                                 C 60.0                                                                    H                                                                                 H  7.4             7797                                                                              CH.sub.3                                                                             CH.sub.3                                                                          CH.sub.3                                                                           CH.sub.3 CH.sub.2                                                                      H  CH.sub.3 S A    (1.4941/24)                                                                          C                                                                                 C 51.1                                                                    H                                                                                 H  8.5                                                                    N                                                                                 N 11.6             7799                                                                              CH.sub.3                                                                             CH.sub.3                                                                          CH.sub.3                                                                           CH.sub.2CHCH.sub.2                                                                     H  CH.sub.3 S A    (1.5017/24)                                                                          C                                                                                 C 53.5                                                                    H                                                                                 H  8.0                                                                    N                                                                                 N 11.2             7803                                                                              CH.sub.3                                                                             CH.sub.3                                                                          CH.sub.3                                                                           CH.sub.3 H  C.sub. 6 H.sub.5 O                                                                       A    128-129                                                                              C                                                                                 C 63.7                                                                    H                                                                                 H  7.7                                                                    N                                                                                 N 10.7             7804                                                                              CH.sub.3                                                                             CH.sub.3                                                                          CH.sub.3                                                                           CH.sub.3 H  CH.sub.3 S(O)                                                                            D    (1.5040/24)                                                                          C                                                                                 C 45.2                                                                    H                                                                                 H  7.5                                                                    N                                                                                 N 11.9             7859                                                                              CH.sub.3                                                                             CH.sub.3                                                                          CH.sub.3                                                                           H        H  CH.sub.3 S B    58-60  C                                                                                 C 46.7                                                                    H                                                                                 H  7.7                                                                    N                                                                                 N 13.5             7870                                                                              CH.sub.3                                                                             CH.sub.3                                                                          CH.sub.3                                                                           CH.sub.3 H  C.sub.4 H.sub.8 N.sup.(b)                                                                C    43-46  N                                                                                 N 17.0             7895                                                                              CH.sub.3                                                                             CH.sub.3                                                                          CH.sub.3                                                                           CH.sub.3 H  CH.sub.3 NHCOO                                                                           A    (1.4796/24)                                                                          C                                                                                 C 49.7                                                                    H                                                                                 H  7.8             7897                                                                              CH.sub.3                                                                             CH.sub.3                                                                          CH.sub.3                                                                           CH.sub.3 H  CH.sub.2CHCH.sub.2 S                                                                     A    (1.5075/25)                                                                          N                                                                                 N 11.9             7934                                                                              CH.sub.3                                                                             CH.sub.3                                                                          CH.sub.3                                                                           CH.sub.3 H  CH.sub.3 S A    (1.4937/24)                                                                          C                                                                                 C 53.2                 CH.sub.2 CH.sub.2                                  H                                                                                 H  8.8                                                                    N                                                                                 N 11.5             7960                                                                              CH.sub.3 S                                                                           CH.sub.3                                                                          CH.sub.3                                                                           CH.sub.3 H  CH.sub.3 S A    (1.5339/24)                                                                          C                                                                                 C 43.7                                                                    H                                                                                 H  7.2                                                                    N                                                                                 N 11.7             7991                                                                              CH.sub.3                                                                             CH.sub.3                                                                          CH.sub.3                                                                           CH.sub.3 H  NCS        C    85-86  C                                                                                 C 47.5                                                                    H                                                                                 H  6.6                                                                    N                                                                                 N 18.8             8018                                                                              CH.sub.3                                                                             CH.sub.3                                                                          CH.sub.3                                                                           CH.sub.3 H  C.sub.6 H.sub.11 S                                                                       C    105-106                                                                              C                                                                                 C 59.1                                                                    H                                                                                 H  9.1                                                                    N                                                                                 N  9.8             8813                                                                              (CH.sub.2).sub.2                                                                         H    CH.sub.3 CH.sub.2                                                                      H  CH.sub.3 S A    (1.5205/24)                                                                          C                                                                                 C 49.8                                                                    H                                                                                 H  7.3             8814                                                                              (CH.sub.2).sub.2                                                                         H    CH.sub.2CHCH.sub.2                                                                     H  CH.sub.3 S A    (1.5296/24)                                                                          N                                                                                 N 12.2             8868                                                                              CH.sub.3                                                                             CH.sub.3                                                                          CH.sub.3                                                                           CH.sub.3 H  CH.sub.3 SO.sub.2                                                                        A    (1.4923/22)                                                                          N                                                                                 N 11.1             9026                                                                              CH.sub.3                                                                             CH.sub.3                                                                          CH.sub.3                                                                           CH.sub.3 H  CH.sub.3 SCH.sub.2 CH.sub.2 S                                                            C    51- 56 C                                                                                 C 47.5                                                                    H                                                                                 H  8.0             9058                                                                              (CH.sub.3).sub.2 CH                                                                  H   H    CH.sub.3 H  CH.sub.3 S A    (1.5005/24)                                                                          C                                                                                 C 49.4                                                                    H                                                                                 H  8.4                                                                    N                                                                                 N 12.7             9071                                                                              (CH.sub.3).sub.2 CH                                                                  H   H    CH.sub.2CHCH.sub.2                                                                     H  CH.sub.3 S A    (1.5035/23)                                                                          C                                                                                 C 54.1                                                                    H                                                                                 H  8.3                                                                    N                                                                                 N 11.3             9072                                                                              CH.sub.3 CH.sub.2                                                                    H   H    CH.sub.2CHCH.sub.2                                                                     H  CH.sub.3 S A    (1.5070/23)                                                                          N                                                                                 N 12.3             9226                                                                              CH.sub.3                                                                             CH.sub.3                                                                          CH.sub.3                                                                           CH.sub.2CHCH.sub.2                                                                     H  CH.sub.3 SCH.sub.2 CH.sub.2 S                                                            A    (1.5285/24)                                                                          C                                                                                 C 51.4                                                                    H                                                                                 H  7.8                                                                    N                                                                                 N  9.4             9300                                                                              CH.sub.3                                                                             CH.sub.3                                                                          CH.sub.3                                                                           CH.sub.3 H  CH.sub.3 O A    (1.4650/24)                                                                          C                                                                                 C 52.8                                                                    H                                                                                 H  9.0             9315                                                                              CH.sub.3                                                                             CH.sub.3                                                                          CH.sub.3                                                                           CH.sub.3 H  CH.sub.3 CH.sub.2 O                                                                      A    (1.4649/24)                                                                          N                                                                                 N 13.4             8031                                                                              CH.sub.3                                                                             CH.sub.3                                                                          CH.sub.3                                                                           CH.sub.3 H  CH.sub.3 COO                                                                             C    48-50  C                                                                                 C 51.8                                                                    H                                                                                 H  7.8                                                                    N                                                                                 N 12.4             8036                                                                              CH.sub.3                                                                             CH.sub.3                                                                          CH.sub.3                                                                           CH.sub.3 H  4-(CH.sub.3).sub.3 CC.sub.6 H.sub.4                                                      C    (1.5348/24)                                                                          C                                                                                 C 64.7                                                                    H                                                                                 H  8.4                                                                    N                                                                                 N   8.4            8070                                                                              CH.sub.3                                                                             CH.sub.3                                                                          CH.sub.3                                                                           CH.sub.3 H  4-CH.sub.3 OC.sub.6 H.sub.4 S                                                            C    90-92  C                                                                                 C 57.6                                                                    H                                                                                 H  7.0                                                                    N                                                                                 N  8.7             8073                                                                              CH.sub.3                                                                             CH.sub.3                                                                          CH.sub.3                                                                           CH.sub.3 H  4-ClC.sub.6 H.sub.4 S                                                                    C    111-112                                                                              C                                                                                 C 53.0                                                                    H                                                                                 H  6.1                                                                    N                                                                                 N  8.9             8169                                                                              (CH.sub.2).sub.5                                                                         H    CH.sub.3 H  CH.sub.3 S A    70-71  C                                                                                 C 54.2                                                                    H                                                                                 H  8.3                                                                    N                                                                                 N 11.8             8179                                                                              (CH.sub.2).sub.5                                                                         CH.sub.3                                                                           CH.sub.3 H  CH.sub.3 S A    (1.5200/25)                                                                          C                                                                                 C 55.7                                                                    H                                                                                 H  8.6             8465                                                                              (CH.sub.2).sub.2                                                                         H    CH.sub.3 H  CH.sub.3 S A    (1.5297/23)                                                                          N                                                                                 N 14.3             8519                                                                              (CH.sub.3).sub.3 C                                                                   H   H    CH.sub.3 H  CH.sub.3 S A    (1.4960/23)                                                                          C                                                                                 C 51.3                                                                    H                                                                                 H  8.5             9337                                                                              CH.sub.3                                                                             CH.sub.3                                                                          CH.sub.3                                                                           CH.sub.3 H  CH.sub.3 CH.sub.2 SCH.sub.2 CH.sub.2                                                     A    (1.5261/23)                                                                          C                                                                                 C 49.8                                                                    H                                                                                 H  8.3             9350                                                                              CH.sub.3                                                                             CH.sub.3                                                                          CH.sub.3                                                                           CH.sub.3 H  CH.sub.3 SO.sub.3                                                                        E    (1.4810/25)                                                                          C                                                                                 C 41.2                                                                    H                                                                                 H  6.8                                                                    N                                                                                 N 10.5             9386                                                                              CH.sub.3                                                                             CH.sub.3                                                                          CH.sub.3                                                                           CH.sub.3 H  F.sub.3 CCH.sub.2 CH.sub.2 S                                                             A    64-66  C                                                                                 C 44.2                                                                    H                                                                                 H  6.5             9387                                                                              CH.sub.3                                                                             CH.sub.3                                                                          CH.sub.3                                                                           CH.sub.3 CH.sub.2                                                                      H  F.sub.3 CCH.sub.2 CH.sub.2 S                                                             A    (1.4623/24)                                                                          C                                                                                 C 46.7                                                                    H                                                                                 H  6.9                                                                    N                                                                                 N  9.0             9388                                                                              CH.sub.3                                                                             CH.sub.3                                                                          CH.sub.3                                                                           CH.sub.2CHCH.sub.2                                                                     H  F.sub.3 CCH.sub.2 CH.sub.2 S                                                             A    (1.4717/24)                                                                          C                                                                                 C 48.7                                                                    H                                                                                 H  6.6                                                                    N                                                                                 N  9.1             9389                                                                              CH.sub.3                                                                             CH.sub.3                                                                          CH.sub.3                                                                           CH.sub.3 H  C.sub.6 H.sub.5 CH.sub.2 CH.sub.2                                                        A    (1.5405/24)                                                                          C                                                                                 C 62.8                                                                    H                                                                                 H  7.8             9391                                                                              CH.sub.3                                                                             CH.sub.3                                                                          CH.sub.3                                                                           CH.sub.2CHCH.sub.2                                                                     H  C.sub.6 H.sub.5 CH.sub.2 CH.sub.2                                                        A    (1.4253/24)                                                                          C                                                                                 C 65.5                                                                    H                                                                                 H  8.1             9425                                                                              CH.sub.3                                                                             CH.sub.3                                                                          CH.sub.3                                                                           CH.sub.3 H                                                                                 ##STR15## A    159-160                                                                              C 60.5 H  6.1 N                                                               13.2                                                                              C 60.2 H  6.1                                                                 N 13.3             9431                                                                              CH.sub.3                                                                             CH.sub.3                                                                          CH.sub.3                                                                           CH.sub.3 H  SCH.sub.2 CH.sub.2 CCl.sub.3                                                             A    87-89  C                                                                                 C 38.7                                                                    H                                                                                 H  5.6                                                                    N                                                                                 N  7.9             9432                                                                              CH.sub.3                                                                             CH.sub.3                                                                          CH.sub.3                                                                           C.sub.2 H.sub.5                                                                        H  SCH.sub.2 CH.sub.2 CCl.sub.3                                                             A    (1.5168/24)                                                                          C                                                                                 C 40.0                                                                    H                                                                                 H  5.9                                                                    N                                                                                 N  7.9             9433                                                                              CH.sub.3                                                                             CH.sub.3                                                                          CH.sub.3                                                                           CH.sub.2CHCH.sub.2                                                                     H  SCH.sub.2 CH.sub.2 CCl.sub.3                                                             A    (1.5228/24)                                                                          C                                                                                 C 42.8                                                                    H                                                                                 H  5.6             9435                                                                              CH.sub.3                                                                             CH.sub.3                                                                          CH.sub.3                                                                           CH.sub.3 H                                                                                 ##STR16## A    64-66                                                                                 ##STR17##                                                                         ##STR18##         9542                                                                              CH.sub.3                                                                             CH.sub.3                                                                          CH.sub.3                                                                           CH.sub.3 H                                                                                 ##STR19## A    (1.5542/24)                                                                          C 52.0 H                                                                          C 52.0 H  6.7      9543                                                                              CH.sub.3                                                                             CH.sub.3                                                                          CH.sub.3                                                                           CH.sub.3 H                                                                                 ##STR20## A    (1.5480/24)                                                                          C 53.5 H                                                                          C 53.6 H  6.9      9544                                                                              CH.sub.3                                                                             CH.sub.3                                                                          CH.sub.3                                                                           H.sub.2 CCHCH.sub.2                                                                    H                                                                                 ##STR21## A    (1.5507/24)                                                                          C 55.2 H                                                                          C 55.7 H  6.8      9901                                                                              CH.sub.3                                                                             CH.sub.3                                                                          CH.sub.3                                                                           CH.sub.3 H                                                                                 ##STR22## A    80-83  C 55.5 H  6.8 N                                                               14.9                                                                              C 54.7 H  6.9                                                                 N 15.2             9902                                                                              CH.sub.3                                                                             CH.sub.3                                                                          CH.sub.3                                                                           C.sub.2 H.sub.5                                                                        H                                                                                 ##STR23## A    92-94  C 56.9 H  7.2 N                                                               14.2                                                                              C 56.6 H  7.4                                                                 N 14.3             9903                                                                              CH.sub.3                                                                             CH.sub.3                                                                          CH.sub.3                                                                           H.sub.2 CCHCH.sub.2                                                                    H                                                                                 ##STR24## A    54-56  C 58.6 H  6.9 N                                                               13.7                                                                              C 58.1 H  7.0                                                                 N 14.0             10629                                                                             CH.sub.3                                                                             CH.sub.3                                                                          CH.sub.3                                                                           CH.sub.2CHCH.sub.2                                                                     H                                                                                 ##STR25## A    118-119                                                                              C 58.6 H  6.9 N                                                               13.7                                                                              C 59.1 H  7.1                                                                 N 13.5             10673                                                                             CH.sub.3                                                                             CH.sub.3                                                                          CH.sub.3                                                                           CH.sub.3 H                                                                                 ##STR26## A    140-142                                                                              C 55.5 H  6.9 N                                                               14.9                                                                              C 55.1 H  6.9                                                                 N 15.6             10879                                                                             CH.sub.3                                                                             CH.sub.3                                                                          CH.sub.3                                                                           CH.sub.3 H                                                                                 ##STR27## C    148-150                                                                              C 45.3 H  7.3 N                                                               14.4                                                                              C 45.0 H  7.3                                                                 N 14.1             10987                                                                             CH.sub.3                                                                             CH.sub.3                                                                          CH.sub.3                                                                           CH.sub.3 H                                                                                 ##STR28## C    149    C 42.5 H  6.2 N                                                               9.9 C 42.5 H  6.2                                                                 N                  __________________________________________________________________________                                                               10.1                *Method:                                                                      A = Example 3                                                                 B = Example 4                                                                 C = Example 5                                                                 D = Example 6                                                                 E = Example 7                                                                 .sup.(a) J. Agr. Food Chem., 14, 356 (1966)                                   .sup.(b) 1-pyrrolidinyl                                                       .sup.(c) hydrochloride salt                                              

The compounds are evaluated for biological activity against thefollowing representative pests: Mexican bean beetle (Epilachnavarivestis), Southern army worm (Prodenia eridania), housefly (Muscadomestica), bean aphid (Aphis fabae), and red spider mite (Tetranychussp.). The last two pests are treated both by contact and systemicapplication.

For purposes of comparison, results obtained with known Compound 7472,Compound 7577, and aldicarb are included in the test results. Each testcompound is rated using the following scale:

    __________________________________________________________________________    Contact Activity     Systemic Activity                                              >-                                                                             50% mortality at    >-                                                                             50% mortality at                                  Rating =                                                                             concentration in                                                                            Rating =                                                                             concentration in                                  Number parts per million of                                                                        Number pounds per acre of                                __________________________________________________________________________    0      500           0      16                                                1      500-250       1      16-8                                              2      250-128       2      8-4                                               3      128-64        3      4-2                                               4      64-32         4      2-1                                               5      32-16         5      1- 1/2                                            6      16-8          6      1/2-1/4                                           7      8-4           7      1/4- 1/8                                          8      4-2           8      1/8- 1/16                                         9      2             9      1/16                                              __________________________________________________________________________

The tests employed are:

EXAMPLE 9 Bean Aphid Spray and Systemic Test

This test determines the insecticidal activity of the compound beingtested against the bean aphid Aphis fabae. Stock formulations containing500 ppm of each test chemical are prepared using 0.05 g of the testchemical (or 0.05 ml of a liquid), 4.0 ml acetone containing 0.25% (V/V)Triton X-155, and 96.0 ml deionized water and are used in both soildrench and spray treatments. The stock formulations are diluted toobtain the appropriate lower concentrations maintaining theconcentration level of all adjuvants. The Bean aphid is cultured onnasturtium plants (var. Tall Single), no attempt being made to selectinsects of a given age in these tests. Single nasturtium test plantsgrowing in soil in individual 21/4 inch fiber pots are fested withpopulations of 100 to 200 aphids.

In the spray application, 50 ml of stock or diluted formulation isuniformly sprayed onto the plants. In the systemic application, 11.2 mlof stock or diluted formulation is applied to the soil containing theplant. A dosage of 11.2 ml of formulation containing 500 ppm of testchemical is equivalent to a dosage of the test chemical of 16 pounds peracre.

The plant test units under fluorescent lights are given bottom wateringfor the duration of the test. Percentage mortality is determined threedays after treatment. Results of this test are shown in Table 4 as A(aphid contact spray) and AS (aphid systemic soil drench).

EXAMPLE 10 Red Spider Mite Spray and Systemic Test

This test determines the acaricidal activity of the compound beingtested against the red spider mite, Tetranychus sp. Stock formulationscontaining 500 ppm of each test chemical are prepared by the proceduredescribed in Example 9 and are used in both the soil drench and spraytreatments. The stock culture of mites is maintained on Scarlet runnerbean foliage. Approximately 18 to 24 hours before testing, mites aretransferred to the primary leaves of two Lima bean plants (var. Sieva)grown in 21/4 inch pots.

The spray and systemic application methods described in Example 10 areused to apply the test formulations to the infested plants and soil.After three days, two of the four leaves treated are examined andmortality is determined. Should a compound be an effective miticide, theother two leaves are available to obtain information on the residualactivity of the formulation. Results of this test are shown in Table 4as M (mite contact spray test) and MS (mite systemic soil drench test).

EXAMPLE 11 Housefly Spray Test

This test determines the insecticidal activity of the compound beingtested against adult houseflies, Musca domestica. Stock formulationscontaining 500 ppm of each test chemical are prepared using theprocedure described in Example 10 and are diluted to obtain theappropriate lower concentrations.

Ten adult flies are placed in a cylindrical screen cage 11/2 by 4 inchesfabricated from 20-mesh stainless steel screening and are sprayed with50 ml of the stock or diluted formulation. The flies are supplied foodand drink from a dextrose solution by draping a paper wick over theoutside of the screen cylinder and are able to feed and drink adlibitum. Percent mortality obtained is determined three days aftertreatment. Results of this test are shown in Table 4 as HF (houseflyspray test).

EXAMPLE 12 Southern Army Worm Spray Test

Paired fully expanded primary leaves excised from Scarlet runner beanplants are maintained in plastic tubes containing water and sprayed withthe test formulation prepared as described in Example 10. After thespray deposit on the leaves is dry, the paired leaves are separated. Oneleaf is placed onto 1.5 percent water agar and infested with 10 newlyhatched Southern army worm larvae. The covered test receptacle is heldat 72° F. for three days and then the percent mortality is determined.Results of this test are shown in Table 4 as AW (Southern army wormspray test).

EXAMPLE 13 Mexican Bean Beetle Leaf Spray Test

This test determines the insecticidal activity of the compound beingtested against the Mexican bean beetle (Epilachna varivestis). The testprocedure is the same as that described for the Southern army worm inExample 12 with the exception that one-day old larvae of the Mexicanbean beetle instead of newly hatched Southern army worm larvae are used.

These tests are held at 72° F. for three days when mortality and feedinginhibition are determined. The feeding inhibition is an indication ofthe repellent properties of the test material. Results of this test areshown in Table 4 as BB (Mexican bean beetle leaf spray test).

                  TABLE 4                                                         ______________________________________                                        Compound                                                                      Number*     BB.sup.1                                                                             AW.sup.2                                                                             HF.sup.3                                                                           M.sup.4                                                                            A.sup.5                                                                            MS.sup.6                                                                           AS.sup.7                        ______________________________________                                        7268        5      0      1    7    9    5    7                               7472        0      0      0    0    1    0    1                               7503        3      0      0    1    6    1    0                               7577        0      0      0    0    0    0    0                               7718        5      0      1    0    2    0    1                               7797        2      0      3    3    5    3    4                               7799        5      0      2    2    5    2    0                               7804        6      2      2    5    8    5    7                               7859        4      0      0    5    7    3    4                               7897        4      0      3    4    4    1    3                               7934        5      0      0    6    6    2    2                               7960        4      0      0    5    5    0    0                               7991        5      0      0    0    2    0    0                               8465        4      1      2    2    5    0    4                               8868        7      0      2    6    8    6    7                               9026        6      0      0    4    4    0    0                               9058        0      0      1    2    7    0    6                               9425        0      0      0    0    0    0    0                               9431        4      0      0    0    1    0    0                               9432        2      0      0    0    0    0    0                               9433        2      0      0    0    1    0    0                               9435        3      2      3    3    4    1    3                               9542        4      0      0    0    2    0    0                               9543        3      0      0    0    0    0    0                               9544        3      0      0    0    0    0    0                               9901        5      0      2    4    6    0    0                               9902        4      0      0    0    3    0    0                               9903        3      0      3    0    3    0    0                               10629       3      0      0    0    0    0    0                               10673       5      0      3    0    3    0    3                               10879       5      0      0    0    0    0    0                               10987       4      0      0    0    0    0    0                               aldicarb    4      0      7    4    9    5    9                               ______________________________________                                         .sup.1 BB = Mexican bean beetle                                               .sup.2 AW = Southern army worm                                                .sup.3 HF = housefly                                                          .sup.4 M = mite contact                                                       .sup.5 A = aphid contact                                                      .sup.6 MS = mite systemic                                                     .sup.7 AS = aphid systemic                                                    *Those compound numbers which are not identified in Table 3, hereinbefore     are identified in Table 6 of USSN 229,207.                               

It is to be noted that Compound 7268 exhibits outstanding activityagainst all of the pests except the Southern army worm and the housefly.This activity is comparable or superior to that of the commercialmaterial, aldicarb (Formula III), and vastly superior to that ofCompound 7472 (Formula I), the unsubstituted 3,3-dimethyl-2-butanonederivative, or Compound 7577 (Formula II), the ketoxime analog ofaldicarb.

The high insecticidal and miticidal activity of Compund 7268 is furtherdemonstrated by the results of special tests described below.

EXAMPLE 14 Systemic Test of Compound 7268 Against Lygus Bug and SpottedCucumber Beetle

The techniques used are essentially the same for the systemic testsdescribed above in Example 10. The test compound is Compound 7268. Thereis one Sieva bean plant per pot and five adult insects are caged on eachplant. One plant is used for each test species. The checks showed nomortality during the tests.

    ______________________________________                                        % Mortality                                                                   Dosage, Lygus Bug       Spotted Cucumber Beetle                               lb/A    3 days  4 days  6 days                                                                              3 days                                                                              4 days                                                                              6 days                              ______________________________________                                        2       100     100     100   60    100   100                                 1        80      80     100   30    100   100                                 0.5      0       60      80   20     40    80                                 ______________________________________                                    

EXAMPLE 15 Activity of Compound 7268 Against Southern Corn Rootworm

The test organism is a strain of Southern corn rootworm (Diabroticaundecimpunctata howardi) resistant to chlorinated hydrocarboninsecticides and test compound is Compound 7268. Duplicate samples ofsand-soil mixtures are treated with appropriate volumes of testformulation to give the desired dosages. The sand-soil samples are incovered paper cups, and several hours after drenching, all cups aregiven a thorough shaking to provide complete and uniform mixing of thechemical throughout the soil. One day after treatment, two cornseedlings and five rootworms are placed into each cup and the lidsreplaced. Five days later, mortality is determined. The results aregiven below:

    ______________________________________                                        Dosage, lb/6" A 2.5       1.25      1                                         % Mortality     100       100       90                                        ______________________________________                                    

EXAMPLE 16 Systemic Activity of Compound 7268 Against Melon Aphid

The techniques used are essentially the same as for the systemic testsdescribed above in Example 10. These test plants are cucumber seedlings;the test compound is Compound 7268; and the pest is the melon aphid(Aphis gosyppi).

    ______________________________________                                        Dosage, lb/A                                                                           0.5       0.25      0.125   0.062                                    % Control                                                                              100       100       100     100                                      ______________________________________                                    

EXAMPLE 17 Residual Systemic Activity of Compound 7268 Against MexicanBean Beetle Larvae

Three furrows are opened in soil contained in 8"× 10"× 3" fiber pans and12 Pinto bean seeds are evenly distributed in each furrow. The testcompound is Compound 7268. Appropriate volumes of test formulation togive the desired dosages are applied over the seeds in the open furrows,and the furrows are immediately closed. At the indicated weeklyintervals, one leaf is harvested from each row, placed onto water agarin a plastic Petri dish, and infested with 10 one-day-old bean beetlelarvae. Mortality is determined three days later.

    ______________________________________                                        Weeks After % Mortality at Indicated Dosage, lb/A                             Treatment   1        0.5      0.25   Check                                    ______________________________________                                        3           100      100      100    0                                        7           100      100      100    10                                       10          95       100      100    0                                        11          95       70       95     0                                        ______________________________________                                    

EXAMPLE 18 Root-knot Nematocide Test

This test is an evaluation of the effectiveness of the compound beingtested against infection by root-knot nematodes (Meloidogyne spp.).

Composted greenhouse soil, diluted by one-third with clean washed sand,is infested with about two grams of knotted or galled tomato roots perpot. Treatment is accomplished by applying 25 ml of the formulatedcompound onto the infested soil. The test formulation contains 0.056 gof Compound 7960, 1.0 ml stock emulsifier solution (0.25% Triton X-155in acetone by volume), and 24.0 ml deionized water, giving aconcentration of 2240 ppm. Lower concentrations are achieved bydilution.

After treatment with the test formulation, the soil, inoculum, andformulation are thoroughly mixed, returned to the pot, and the mixtureincubated for seven days at 20° C. and constant moisture. Afterincubation, two seedlings of Rutgers tomato transplants and three gardennasturtium (Nasturtium spp.) seeds are set in each pot. Roots areremoved from the soil after three weeks of growth and rated for gall(root-knot nematode infection) formation. Nasturtium roots are evaluatedonly when necrosis of the tomato host has occurred. A rating ofinfection from 0 to 10 is recorded: 0= no galls or complete control, and10= heavily galled roots comparable to controls. Each of the rootsystems is rated separately and the average is multiplied by 10 andsubtracted from 100 to give percent nematode control. Results of thetests are shown below:

    ______________________________________                                        Compound                                                                              Percent Control at Indicated Dosage, lb/A                             Number  8        4        2      1      0.5                                   ______________________________________                                        7960    100      100      100    100    97                                    8423    100      90       60     --     --                                    8997    100      100      0      --     --                                    9026    90       70       60     30     --                                    ______________________________________                                    

It is to be understood that although the invention has been describedwith specific reference to particular embodiments thereof, it is not tobe so limited, since changes and alterations therein may be made whichare within the full intended scope of this invention as defined by theappended claims.

What is claimed is:
 1. A composition of matter having the formula:##STR29## where: R₁ =R₂ -R₃ or hydrogen;R₂ -r₃ =lower alkyl, loweralkenyl, lower alkynyl, with the proviso that R₂ and R₃ may be connectedto form a cycloaliphatic ring; R₄ -r₅ =hydrogen; R₆ -r₇ =hydrogen, loweralkyl, lowr alkenyl, or lower alkynyl;where m and n may be the same ordifferent, and each is = 0, 1, or 2, R₈ is a lower alkylene radical; andR₉ is selected from the group consisting of hydrogen, lower alkyl, loweralkenyl, lower alkynyl, aryl, or haloalkyl.
 2. The composition of matteraccording to claim 1 wherein said composition of matter is selected fromthe group consistingof:3,3-dimethyl-2-methylcarbamyloximino-1-(2-methylthioethylthio)butane;3,3-dimethyl-2-methylcarbamyloximino-1-(methylthiomethylthio)-butane;3,3-dimethyl-2-methylcarbamyloximino-1-(2-ethylthioethylthio)-butane;3,3-dimethylcarbamyloximino-1-(ethylthiomethylthio)-butane.
 3. Thecomposition of matter according to claim 1 wherein X is CH₃ CH₂ SCH₂ CH₂S--.